EP3631057B1 - Fibres de polycétone, leur preparation et leur utilisation - Google Patents

Fibres de polycétone, leur preparation et leur utilisation Download PDF

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Publication number
EP3631057B1
EP3631057B1 EP18728303.1A EP18728303A EP3631057B1 EP 3631057 B1 EP3631057 B1 EP 3631057B1 EP 18728303 A EP18728303 A EP 18728303A EP 3631057 B1 EP3631057 B1 EP 3631057B1
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EP
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Prior art keywords
polyphenylene
melt
polymer
fibers
aliphatic polyketone
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EP18728303.1A
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German (de)
English (en)
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EP3631057A1 (fr
Inventor
Andreas Hilmar Fischer
Pascal Heckenbenner
Benedikt NEUGIRG
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Perlon GmbH
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Perlon GmbH
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Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/96—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from other synthetic polymers
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D01D5/082—Melt spinning methods of mixed yarn
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/30—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising olefins as the major constituent
    • A—HUMAN NECESSITIES
    • A46—BRUSHWARE
    • A46D—MANUFACTURE OF BRUSHES
    • A46D1/00—Bristles; Selection of materials for bristles
    • A—HUMAN NECESSITIES
    • A46—BRUSHWARE
    • A46D—MANUFACTURE OF BRUSHES
    • A46D1/00—Bristles; Selection of materials for bristles
    • A46D1/02—Bristles details
    • A46D1/0207—Bristles characterised by the choice of material, e.g. metal
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/16—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated carboxylic acids or unsaturated organic esters, e.g. polyacrylic esters, polyvinyl acetate
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/06—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyolefin as constituent
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/12—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyamide as constituent
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent

Definitions

  • the present invention relates to melt-spun fibers made from selected polyketone-containing compositions, their production and various applications of these fibers.
  • Synthetic threads made from melt-spinnable polymers are preferred for technical applications.
  • long-known standard polymers for example polyolefins such as polyethylene (PE), polypropylene (PP), polyamides such as polyamide 6 (PA 6), polyamide 6.6 (PA 6.6) or polyesters such as polyethylene terephthalate ( PET), provided threads made from these polymers can meet the desired requirements.
  • low sliding friction is often desired for textile fabrics.
  • Additional properties are often desired, such as a specific coloring, stability against degradation due to thermal stress or exposure to radiation, special mechanical properties such as increased impact strength, low elongation at break, increased abrasion resistance, dimensional stability, flexural strength or flexural recovery.
  • Fibers made from aliphatic polyketones and from combinations of aliphatic polyketones with selected other polymers are known.
  • EP 0 310 171 A2 describes melt-spun fibers made from these materials, for example from ethylene/propylene/CO terpolymers. These fibers have high tensile strengths and moduli of elasticity and are suggested for use as tire cord or for the production of spunbonds. The latter are suitable for producing roof underlayment or as geotextiles.
  • Aliphatic polyketones are known, which exist, among other things, as fibers and which can be stabilized with antioxidants.
  • CN 106 521 704 A describes mixtures of aliphatic polyketones and polyoxymethylene, which can be present, among other things, as fibers and which can be stabilized with antioxidants. Multicomponent fibers are not disclosed.
  • WO 2016/190594 A2 and WO 2016/190596 A2 disclose wet-spun fibers made of ethylene/propylene/-CO terpolymers which have excellent strength and elongation values and which are also characterized by high water and heat resistance and good thermal conductivity.
  • Various uses are suggested for these fibers, for example the production of ropes, hoses, nets, spunbonds, airbags or protective clothing. as well as use as geotextiles, as reinforcing fibers in composite materials, as straps, safety nets, conveyor belts, fishing lines or tennis strings.
  • thermoplastic polymer is a polyester, polyamide, polyetherketone, polyphenylene sulfide, polyolefin, or a combination of two or more thereof. However, these are not aliphatic polyketones.
  • WO0020512 A1 describes a polymer mixture consisting of a linear polyketone, a polyolefin and a compatibilizer for thermoplastic polyurethane.
  • the polymer blend can be processed into articles, films, sheets, coatings, liners, fibers or monofilaments with improved mechanical properties, but the polymer blend does not include polymer combinations consistent with the present application.
  • the dissolved polymer is spun into threads through a spinning capillary.
  • the solvent is recovered as completely as possible and returned to the manufacturing process.
  • higher degrees of crystallization can be achieved through melt spinning, which can have a beneficial effect on the mechanical properties of the fiber.
  • thermomechanical properties of the fibers could be specifically improved, such as: whose Heat resistance, hydrolysis resistance, chemical resistance, abrasion resistance, flexural strength, flexural recovery, modulus, creep behavior and bending tendency.
  • Dimensional stability describes the tendency of a fiber to show a change in length under tension and at a certain temperature. It results from a combination of the tensile modulus and the creep properties of the fiber, for example a monofilament.
  • aliphatic polyketone-based fibers can be achieved through appropriate additives.
  • Selected polymeric additives can be used that are dispersed in the matrix of aliphatic polyketone.
  • fibrils can form from the dispersed phase and/or the surface of the fiber is modified by the dispersed phase.
  • the individual polymer components complement each other in a synergistic manner.
  • the other polymers give the fibers excellent mechanical properties (high modulus, low creep, low tendency to bend) and the aliphatic polyketone gives them low sliding friction and increased abrasion resistance.
  • the yarns made of aliphatic polyketone or multi-component yarns with aliphatic polyketone as a cover and with the other polymer as a core have a very low sliding friction and a very high abrasion resistance in dry as well as in wet conditions exhibit.
  • fibers made from selected conventional polymers can be combined with aliphatic polyketones to form fibers that are characterized by low sliding friction and high flexural strength.
  • Multi-component fibers with selected properties can be obtained, for example fibers with core/sheath structures, where the sheath consists of aliphatic polyketone and the core consists of polyester, for example polyethylene terephthalate or polycarbonate or aliphatic polyketone with a higher melting point than the aliphatic polyketone of the sheath .
  • the melting points of the sheath polymer for example, adhesive properties can be specifically adjusted.
  • core-sheath fibers with high chemical resistance can be produced.
  • Hot melt variants with a low melting point and thus possible thermal bonding with a substrate or with other monofilaments in a textile construct, e.g. in woven or knitted fabrics, can therefore be produced.
  • fibers are created with low coefficients of friction and very good abrasion resistance.
  • An object of the present invention is to provide such fibers with the above-mentioned property profile.
  • Another object of the present invention is to provide a spinning process for producing such fibers.
  • the present invention relates to melt-spun fibers containing thermoplastic aliphatic polyketone as the first polymer and polyolefin, polyester, polyamide, polyoxymethylene, polyurethane, polyphenylene sulfide, polyphenylene sulfone, polyphenylene ether, polyphenylene ketone, polyphenylene ether ketone, liquid crystalline polymer and / or aliphatic polyketone as the second polymer, wherein the polymers are in the form of two or more fiber components, which are spatially separated from one another but are arranged contiguously and, in the event that aliphatic polyketone is included as the second polymer, its melting point is at least 5 ° C, preferably at least 10 ° C, especially is preferably at least 20 ° C higher than the melting point of the aliphatic polyketone of the first polymer.
  • the present invention also relates to melt-spun fibers containing thermoplastic aliphatic polyketone as a matrix polymer and particles of polysiloxanes or poly(meth)acrylates dispersed therein.
  • the aliphatic polyketones used according to the invention are homo- or copolymers with recurring structural units of the formula -R 1 -CO-, where R 1 represents a divalent aliphatic radical, preferably a divalent aliphatic radical with two to six carbon atoms.
  • R 1 represents a divalent aliphatic radical, preferably a divalent aliphatic radical with two to six carbon atoms.
  • Preferred radicals R 1 have the formula -C n H 2n -, in which n is 2, 3 or 4, in particular 2 or 3.
  • Copolymers with different radicals R 1 in the polymer chain are preferably used, for example with radicals -C 2 H 4 - and with radicals -C 3 H 7 -.
  • thermoplastic ethylene/propylene/CO terpolymer is particularly preferably used as the aliphatic polyketone.
  • Aliphatic polyketones are semi-crystalline polymers that have a melting point in differential thermal analysis (DSC).
  • DSC analysis is performed according to ASTM D3418. The heating rate is 10 K/min.
  • Aliphatic polyketones with a melting range of 199 to 220 ° C and with an MFI value at 240 ° C and 2.16 daN of 6 to 60 g / 10 min (according to ASTM-D 1238) are also particularly preferably used.
  • the aliphatic polyketones used according to the invention are polymers known per se and have also already been used for fiber production.
  • melt-spun fibers according to the invention contain an antioxidant.
  • Sterically hindered phenols and/or HALS (hindered amine light stabilizer) and/or phosphites can be used as antioxidants, which are optionally combined with co-stabilizers.
  • antioxidants based on sterically hindered phenols are sterically hindered alkylated monophenols, for example 2,6-di-tert-butyl-4-methylphenol or 2,6-di-tert-butyl-4-methoxyphenol; sterically hindered alkylthiomethylphenols, e.g. 2,4-di-octylthiomethyl-6-tert-butylphenol, sterically hindered hydroxylated thiodiphenyl ethers, e.g.
  • dioctadecyl 2,2-bis-(3,5-di-tert-butyl-2-hydroxy-benzyl)-malonate sterically hindered hydroxybenzyl aromatics, e.g. 1, 3,5-Tris-(3,5-di-tert-buty)-4-hydroxy-benzyl)-2,4,6-trimethylbenzene, 1,4-bis-(3,5-di-tert-butyl- 4-hydroxy-benzyl)-2,3,5,6-tetramethylbenzene, 2,4,6-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-phenol; sterically hindered phenolic triazine compounds, e.g. B.
  • the preferred co-stabilizers include organic phosphites and/or organic phosphonites. These are known co-stabilizers for antioxidants.
  • the antioxidant content is usually between 0.05 and 10% by weight, based on the total mass of the fiber. Antioxidant proportions of 0.1 to 5% by weight, in particular 0.5 to 3% by weight, are preferred.
  • the fibers according to the invention contain, in addition to the thermoplastic aliphatic polyketone as the first polymer, at least one polyolefin, polyester, polyurethane, polyphenylene sulfide, polyphenylene sulfone, polyphenylene ether, polyphenylene ketone, polyphenylene ether ketone, liquid crystalline polymer and/or another aliphatic polyketone as the second polymer.
  • polyamide and/or polyoxymethylene can also be used as the second polymer.
  • the proportion of aliphatic polyketone as the first polymer in the fibers according to the invention is usually between 5 and 90% by weight, based on the total mass of the fiber. Proportions of aliphatic polyketone as the first polymer of 10 to 80% by weight, in particular 20 to 50% by weight, are preferred.
  • the proportion of polyolefin, polyester, polyurethane, polyphenylene sulfide, polyphenylene sulfone, polyphenylene ether, polyphenylene ketone, polyphenylene ether ketone, liquid crystalline polymer, further aliphatic polyketone, polyamide and / or polyoxymethylene as the second polymer in the Fibers according to the invention is usually between 10 and 95% by weight, based on the total mass of the fiber.
  • polyolefins, polyesters, polyurethanes, polyphenylene sulfides, polyphenylene sulfones, polyphenylene ethers, polyphenylene ketones, polyphenylene ether ketones, liquid-crystalline polymers, other aliphatic polyketones, polyamides and/or polyoxymethylenes used according to the invention are polymers known per se and have also already been used for fiber production.
  • polyolefins are homo- or copolymers derived from ethylene and/or from propylene, optionally in combination with other ethylenically unsaturated aliphatic hydrocarbons, such as ⁇ -olefins with four to eight carbon atoms.
  • Polyethylene and polypropylene can come in different densities and crystallinities. All of these modifications are fundamentally suitable for use according to the invention.
  • polyesters are thermoplastic polymers derived from aliphatic, cycloaliphatic and/or aromatic dicarboxylic acids or their polyester-forming derivatives, such as the alkyl esters, and from aliphatic, cycloaliphatic and/or aromatic dihydric alcohols, such as ethylene glycol, propylene glycol and/or butylene glycol.
  • polyesters are thermoplastic-elastomeric polyesters (TPE-PE), for example polyesters containing recurring ethylene terephthalate structural units and containing recurring polyethylene glycol terephthalate structural units.
  • TPE-PE thermoplastic-elastomeric polyesters
  • polyesters are polycarbonates. These are preferred. Polycarbonates are formally polyesters of carbonic acid containing the repeating structural unit -[R-O-CO-O]-, where R is a residue of a dihydric organic alcohol or phenol after removal of the two alcohol groups. R is preferably the residue of an aromatic dihydroxy compound, i.e. a bisphenol.
  • Preferred radicals R are derived from 2,2-bis-(4-hydroxyphenyl)-propane (bisphenol A), bis-(4-hydroxyphenyl)-methane (bisphenol F), bis-(4-hydroxyphenyl)-sulfone (bisphenol S), dihydroxydiphenyl sulfide, tetramethylbisphenol A or 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (BPTMC).
  • bisphenol A 2,2-bis-(4-hydroxyphenyl)-propane
  • bisphenol F bis-(4-hydroxyphenyl)-methane
  • bisphenol S bis-(4-hydroxyphenyl)-sulfone
  • BPTMC 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane
  • the properties of the resulting polycarbonate can be varied. Cocondensates made from bisphenol A and BPTMC lead to highly transparent and heat-resistant plastics. The incorporation of higher functional alcohols/phenols is also possible, for example 1,1,1-tris(4-hydroxyphenyl)ethane (THPE). This enables the installation of chain branches, which have a positive influence on the structural viscosity when processing the material.
  • THPE 1,1,1-tris(4-hydroxyphenyl)ethane
  • Aromatic-aliphatic polyester homo- or copolymers are also preferably used. Examples of this are polyethylene terephthalate homopolymers or copolymers containing ethylene terephthalate units. These preferred polymers are therefore derived from ethylene glycol and optionally other alcohols as well as from terephthalic acid or the like polyester-forming derivatives, such as terephthalic acid esters or chlorides.
  • these polyesters can contain structural units derived from other suitable dihydric alcohols. Typical representatives of this are aliphatic and/or cycloaliphatic diols, for example propanediol, 1,4-butanediol, cyclohexanedimethanol or mixtures thereof.
  • these polyesters can contain structural units derived from other suitable dicarboxylic acids or from their polyester-forming derivatives. Typical representatives of these are aromatic and/or aliphatic and/or cycloaliphatic dicarboxylic acids, for example naphthalenedicarboxylic acid, isophthalic acid, cyclohexanedicarboxylic acid, adipic acid, sebacic acid or mixtures thereof.
  • Fibers containing other polyesters such as polybutylene terephthalate, polypropylene terephthalate, polyethylene naphthalate homopolymer or copolymers containing ethylene naphthalate units, can also be produced.
  • thermoplastic polyesters are known per se.
  • the building blocks of thermoplastic copolyesters are preferably the above-mentioned diols and dicarboxylic acids, or correspondingly structured polyester-forming derivatives.
  • Polyesters are preferably used whose solution viscosities (IV values) are at least 0.60 dl/g, preferably from 0.80 to 1.05 dl/g, particularly preferably from 0.80 - 0.95 dl/g ( measured at 25°C in dichloroacetic acid (DCE)).
  • IV values solution viscosities
  • Polyesters used according to the invention can also be derived from hydroxycarboxylic acids.
  • thermoplastic-elastomeric polyamides for example polyamides containing recurring hexamethylene terephthalamide structural units and containing recurring polyethylene glycol terephthalamide structural units.
  • TPE-PA thermoplastic-elastomeric polyamides
  • Polyamides used with preference are partially crystalline aliphatic polyamides, which can be prepared starting from aliphatic diamines and aliphatic dicarboxylic acids and/or cycloaliphatic lactams with at least 5 ring members or corresponding amino acids.
  • the starting materials used are aliphatic dicarboxylic acids, preferably adipic acid, 2,2,4- and 2,4,4-trimethyladipic acid, azelaic acid and/or sebacic acid, aliphatic diamines, preferably tetramethylenediamine, hexamethylenediamine, 1,9-nonanediamine, 2,2,4- and 2,4,4-trimethylhexamethylenediamine, the isomeric diaminodicyclohexylmethane, diaminodicyclohexylpropane, bis-aminomethylcyclohexane, aminocarboxylic acids, preferably aminocaproic acid or the corresponding lactams. Copolyamides made from several of the monomers mentioned are included. Caprolactams are particularly preferred, and ⁇ -caprolactam is particularly preferred.
  • the aliphatic homo- or copolyamides used according to the invention are preferably polyamide 12, polyamide 4, polyamide 4.6, polyamide 6, polyamide 6.6, polyamide 6.9, polyamide 6.10, polyamide 6.12, polyamide 6.66, polyamide 7.7, polyamide 8.8, polyamide 9.9, Polyamide 10.9, Polyamide 10.10, Polyamide 11 or Polyamide 12.
  • Polyesters and polyamides used according to the invention can also be derived from hydroxycarboxylic acids or aminocarboxylic acids.
  • polyoxymethylenes that can be used in the second embodiment of the invention are homo- or copolymers containing repeating structural units of the formula -CH 2 -O-.
  • polyurethanes are homo- or copolymers derived from aromatic or (cyclo)aliphatic diisocyanates and from (cyclo)aliphatic or aromatic diols.
  • Polyurethanes for example, contain recurring structural units of the formula -C 6 H 4 -NH-CO-OC 2 H 4 -O-CO-NH-.
  • thermoplastic-elastomeric polyurethanes are known to those skilled in the art.
  • polyphenylene sulfides are poly-p-phenylene sulfides, for example homo- or copolymers containing recurring structural units -para-C 6 H 4 -S-.
  • polyphenylene sulfones examples include poly-p-phenylene sulfones, for example homo- or copolymers containing recurring structural units -para-C 6 H 4 -SO x -, where x is a number between 1 and 2.
  • polyphenylene ethers examples include poly-p-phenylene ethers, for example homo- or copolymers containing recurring structural units -para-C 6 H 4 -O-.
  • polyphenylene ketones are poly-p-phenylene ketones, for example homo- or copolymers containing recurring structural units -para-C 6 H 4 -CO-.
  • polyphenylene ether ketones are poly-p-phenylene ether ketones, for example copolymers containing recurring structural units -para-C 6 H 4 -CO- and recurring structural units -para-C 6 H 4 -O-.
  • liquid-crystalline polymers are liquid-crystalline aromatic polyesters, for example homo- or copolymers containing recurring structural units derived from para-hydroxybenzoic acid.
  • the first polymer and the second polymer can be present as a polymer mixture or the polymers can be in the form of two or more fiber components which are spatially separated from one another but arranged contiguously with one another.
  • Fibers in which the first polymer and the second polymer are present as a polymer mixture are preferred, with one of the polymers, preferably the aliphatic polyketone, forming a matrix and the other polymer being dispersed in the matrix in the form of fibrils.
  • Examples of this embodiment are fibers in the form of island-in-sea fibers, in which a polymer component is arranged in the form of fibrils in the polymeric matrix component.
  • the fibrils are preferred aligned in the longitudinal direction of the fiber and thereby increase the tensile strength and modulus of the fiber.
  • Multicomponent fibers can be mentioned as examples of fibers in which the polymers are present in the form of two or more fiber components that are spatially separated from one another but arranged contiguously with one another.
  • the at least two polymers in the fiber according to the invention can therefore be present as a polymer mixture or the at least two polymers can be in the form of two or more fiber components which are spatially separated from one another but arranged contiguously with one another.
  • Examples of this latter embodiment are multicomponent fibers, which can be present, for example, as core-sheath fibers or as side-by-side fibers.
  • Fibers containing a mixture of aliphatic polyketone and polycarbonate are preferred.
  • fibers in which the aliphatic polyketone forms a polymer matrix and a further polymer selected from the group of polyolefins, polyesters, polyphenylene ketones, polyphenylene ether ketones and/or liquid crystalline polymers in the form of fibrils are present in the polymer matrix component.
  • these fibers contain a liquid-crystalline polymer as an additional polymer.
  • core-sheath fibers with a sheath made of aliphatic polyketone and with a core made of polyolefin, polyester, polyurethane, polyphenylene sulfide, polyphenylene sulfone, polyphenylene ether, polyphenylene ketone, polyphenylene ether ketone, liquid crystalline polymer, further aliphatic polyketone, polyamide and / or polyoxymethylene, whereby for the case that aliphatic polyketone is present in the core, the melting point of which is at least 5 ° C, preferably at least 10 ° C and in particular at least 20 ° C higher than the melting point of the aliphatic polyketone in the shell.
  • Core-sheath fibers with a sheath made of aliphatic polyketone and with a core made of polyester, polyphenylene sulfide, polyphenylene ether, polyphenylene ketone or polyphenylene ether ketone are particularly preferred.
  • side-by-side fibers with a fiber part made of aliphatic polyketone and with a further fiber part in contact with it made of polyolefin, polyester, polyphenylene sulfide, polyphenylene sulfone, polyphenylene ether, polyphenylene ketone, polyphenylene ether ketone, liquid crystalline polymer, further aliphatic polyketone, polyamide and/or or polyoxymethylene, whereby in the event that aliphatic polyketone is present in the further fiber part, the melting point of which is at least 5 ° C, preferably at least 10 ° C and in particular at least 20 ° C higher than the melting point of the aliphatic polyketone in the other fiber part.
  • side-by-side fibers with a fiber part made of aliphatic polyketone and with another fiber part in contact with it made of polyester, polyphenylene sulfide, polyphenylene ether, polyphenylene ketone or polyphenylene ether ketone.
  • side-by-side fibers with a fiber part made of aliphatic polyketone and with a further fiber part in contact with it made of polyolefin, polyester, polyphenylene sulfide, polyphenylene sulfone, polyphenylene ether, polyphenylene ketone, polyphenylene ether ketone and / or liquid crystalline polymer.
  • core-sheath fibers in which the sheath contains aliphatic polyketone as a polymer and the core contains one or more of the above-mentioned second polymers and the core and/or the sheath additionally contains at least one additive which gives the fiber a certain functionality gives.
  • one fiber part contains aliphatic polyketone as a polymer and the other fiber part contains one or more of the above-mentioned second polymers and additionally at least one additive which gives the fiber a certain functionality.
  • core-sheath fibers with a sheath made of aliphatic polyketone and with a core made of further aliphatic polyketone, the melting point of which is at least 5 ° C, preferably at least 10 ° C and in particular at least 20 ° C higher than the melting point of the aliphatic polyketone in the sheath .
  • core-sheath structures with cores made of polyesters, such as PET or polycarbonate, or of aliphatic polyketones with a higher melting point than the sheath polymer can be used to produce fibers with good thermal stability.
  • these are characterized by high tensile and bending moduli and therefore by high stability, for example in core-sheath fibers with PET in the sheath. These fibers often show good dimensional stability under tension at temperatures up to 150°C.
  • fibers are provided in which the fiber surface is modified by selected polymer particles that are dispersed in the matrix polymer.
  • Functionalization and texturing of the surface can be achieved by adding polysiloxane particles, such as PMSQ particles and/or poly(meth)acrylate particles, such as cross-linked PMMA microspheres. Typical diameters of these particles range from 0.2 to 100 ⁇ m.
  • microtexturing of the surface can be created and the surface properties of the fiber can be modified. Above all, this reduces the friction surface and significantly improves the friction properties. In addition, the cleaning properties of the fiber are improved.
  • the invention relates to fibers, in particular monofilaments, containing a matrix of aliphatic polyketone and particles of polysiloxane and/or poly(meth)acrylate distributed therein, which have a diameter of 200 nm to 100 ⁇ m.
  • the particles can have any shape. Examples of this are particles with a rotationally symmetrical shape, especially spheres, but also with an irregular shape. These particles are present as micropowders.
  • the diameter of these particles ranges from 0.2 to 100 ⁇ m, preferably from 1 to 50 ⁇ m. For particles with varying diameters, the diameter information refers to the largest diameter of the particle.
  • Monofilaments are preferred and contain spherical particles made of polysiloxane with a diameter of 1 to 50 ⁇ m.
  • the particles are present as micropowders dispersed in the matrix polymer. In general, 0.001% by weight to 8% by weight, preferably 0.02% by weight to 5% by weight, of particles are metered into the matrix polymer.
  • the particles are present in the matrix polymer as a heterogeneous phase.
  • the particles can be present as individual particles in the matrix polymer and/or as aggregates of various individual particles.
  • the polysiloxanes used according to the invention are a group of synthetic polymers in which silicon atoms are linked via oxygen atoms.
  • the polysiloxanes used according to the invention are also called silicones. These can be linear or cross-linked polysiloxanes or polysiloxanes with a cage structure, so-called silsesquioxanes.
  • Monofilaments which contain polysiloxanes, which are linear or crosslinked polydimethylsiloxanes or a polymethylsilsesquioxane, are very particularly preferred.
  • the poly(meth)acrylates used according to the invention are a group of synthetic polymers which are derived from esters of acrylic acid and/or from esters of methacrylic acid.
  • poly(meth)acrylates can have further monomer units copolymerized with esters of acrylic acid and/or with esters of methacrylic acid.
  • the poly(meth)acrylates used according to the invention can be linear or preferably cross-linked poly(meth)acrylates.
  • Homo- or copolymers of methyl acrylate or methyl methacrylate are preferably used as poly(meth)acrylates.
  • additives are electrically conductive additives, lubricants, anti-adhesive agents, blowing agents for producing foamed or porous fiber surfaces, pigments and/or fillers.
  • Preferred multi-component fibers contain a part made of aliphatic polyketone and a further part in contact with it made of one of the above-mentioned polymer types, in particular polyester, very particularly preferably TPE-PE, or in particular polyurethane, very particularly preferably TPE-PU, the aliphatic polyketone being mainly the Sliding properties improved and the second polymer component mainly improved other properties, such as.
  • B improved grip properties provided, for example, by TPE-PE or TPE-PU or hot-melt adhesive properties provided, for example, by co-polyester.
  • the aliphatic polyketones used according to the invention and/or the other polymers selected from the group consisting of polyolefin, polyester, polyurethane, polyphenylene sulfide, polyphenylene sulfone, polyphenylene ether, Polyphenylene ketone, polyphenylene ether ketone, liquid crystalline polymer, other aliphatic polyketone, polyamide and / or polyoxymethylene can contain additional additives which give the fibers produced a desired property.
  • additives examples include UV stabilizers, pigments, dyes, fillers, matting agents, reinforcing materials, crosslinking agents, crystallization accelerators, lubricants, flame retardants, antistatic agents, hydrolysis stabilizers, plasticizers, impact modifiers and/or other polymers that are different from aliphatic polyketones, polyolefins, polyesters, Polyphenylene sulfides, polyphenylene sulfones, polyphenylene ethers, polyphenylene ketones, polyphenylene ether ketones, liquid crystalline polymers, other aliphatic polyketones, polyamides and/or polyoxymethylenes. These additives are known to those skilled in the art.
  • UV stabilizers examples include UV-absorbing compounds, such as benzophenones or benzotriazoles, or compounds of the HALS type ("hindered amine light stabilizer").
  • Examples of preferred pigments are carbon black, titanium dioxide or iron oxides.
  • Examples of preferred dyes are anionic dyes, acid dyes, metal complex dyes, cationic or basic dyes and disperse dyes.
  • Examples of preferred fillers are carbonates, such as chalk or dolomite, silicates, such as talc, mica, kaolin or sulfates, such as barite, or oxides and hydroxides, such as quartz powder, crystalline silica, aluminum or magnesium hydroxides or magnesium, zinc or calcium oxides). .
  • An example of a preferred matting agent is titanium dioxide.
  • An example of a preferred reinforcing material is glass fibers.
  • crosslinking agents are polyhydric carboxylic acids and their esters, polyhydric alcohols, polycarbonates or polycarbodiimides.
  • crystallization accelerators examples include carboxylic acid esters.
  • lubricants are polyolefin waxes, fatty acids or their salts, fatty alcohols, fatty acid esters, silicones, polymethacrylate beads, polysiloxanes and in particular PMSQ, as in EP 2,933,361 A1 described.
  • Examples of preferred flame retardants are phosphorus-containing compounds, organic halogen compounds, nitrogen-containing organic compounds or combinations thereof.
  • Examples of preferred antistatic agents are carbon black, graphite, graphene or carbon nanotubes.
  • hydrolysis stabilizers examples include carbodiimides or epoxidized compounds.
  • processing aids are waxes or longer-chain carboxylic acids or their salts, aliphatic, aromatic esters or ethers.
  • plasticizers examples include diethylhexyl phthalate, alkylsulfonic acid esters of phenol, triethyl citric acid, diethylhexyl adipate or diethyl octyl adipate.
  • thermoplastic elastomers such as thermoplastic copolyamides, thermoplastic polyester elastomers, thermoplastic copolyesters, olefin-based thermoplastic elastomers, styrene copolymers, such as SBS, SEBS, SEPS, SEEPS, MBS, ABS, SAN or SBK, urethane-based thermoplastic elastomers, thermoplastic Vulcanizates or crosslinked thermoplastic elastomers based on olefins, especially PP/EPDM, or polycarbonate.
  • thermoplastic elastomers such as thermoplastic copolyamides, thermoplastic polyester elastomers, thermoplastic copolyesters, olefin-based thermoplastic elastomers, styrene copolymers, such as SBS, SEBS, SEPS, SEEPS, MBS, ABS, SAN or SBK, urethane-based thermoplastic elastomers, thermoplastic Vulcanizates or crosslinked thermoplastic elast
  • fluoropolymers such as polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer or polychlorotrifluoroethylene.
  • the proportion of these additional additives in the fiber according to the invention can usually be up to 10% by weight, based on the total mass of the fiber. These additional additives are preferably used in amounts of 1 to 5% by weight.
  • the present invention relates to melt-spun core-sheath fibers containing a sheath made of thermoplastic ethylene/propylene/CO terpolymer and a core made of polyolefin, polyester, polyurethane, polyphenylene sulfide, polyphenylene sulfone, polyphenylene ether, polyphenylene ketone, polyphenylene ether ketone, liquid crystalline polymer, etc aliphatic polyketone, polyamide and/or polyoxymethylene, the mass of the shell being 5 to 50% by weight and the mass of the core being 95 to 5% by weight, and wherein the core and/or the shell may also have a total of up to 10% % by weight of additives, in particular sterically hindered phenol, UV stabilizers, pigments, dyes, fillers, matting agents, crosslinking agents, crystallization accelerators, lubricants, flame retardants, antistatic agents, Hydrolysis stabilizers, plasticizers, impact modifier
  • additives in
  • fiber is to be understood as meaning a linear structure that is thin in relation to its length. Typically, the length to diameter ratio of a fiber is at least 5:1. Fibers in the sense of this description can be endless (and are then called filaments) and can be cut to finite length (and are then called bristles or short-cut fibers). Fibers may also be in the form of multiple filaments or in the form of multiple staple fibers. The invention preferably relates to fibers in the form of monofilaments, bristles or short-cut fibers.
  • the cross-sectional shape of the fibers according to the invention can be arbitrary. They can be irregular cross-sections, point- or axis-symmetrical cross-sections, for example round, oval or n-square cross-sections, where n is greater than or equal to 3.
  • the cross-sectional shape of the fibers can also be multilobal.
  • the strength (titer) of the fibers according to the invention can be expressed by the thread weight.
  • 1 dtex corresponds to a fiber mass of 1 g per 10 km of fiber length.
  • Typical thread weights range from 1 to 100,000 dtex.
  • the titer of the monofilaments, bristles or short-cut fibers preferred according to the invention is preferably at least 10 dtex and can fluctuate within wide ranges.
  • Preferred titers of monofilaments, bristles or short-cut fibers are in the range from 10 to 30,000 dtex, in particular in the range from 45 to 20,000 dtex.
  • the components required to produce the fibers according to the invention are known per se, some are commercially available or can be produced by processes known per se.
  • the fibers according to the invention are preferably used for the production of textile fabrics, in particular wovens, laid fabrics, knitted fabrics, braids or crocheted fabrics. These fabrics are manufactured using known techniques.
  • the fibers according to the invention can be produced by a basically known melt spinning process, combined with single or multiple stretching and fixing of the fibers obtained.
  • the invention also relates to a process of the polyketone fibers described above.
  • polyketone raw material is metered into an extruder together with the sterically hindered phenol and pressed in melted form through a die plate.
  • the nozzle plate can have one or more spinning capillaries.
  • the resulting filament is pulled off the spinning capillary.
  • the take-off speed is usually 1 to 120 m/min, in particular 5 to 50 m/min.
  • the sterically hindered phenol and/or further additives can be metered in in the form of a masterbatch which contains the additive(s) and a thermoplastic polymer, the polymer being selected from the group consisting of polyolefin, polyester, polyurethane, polyphenylene sulfide, polyphenylene sulfone , polyphenylene ether, polyphenylene ketone, Polyphenylene ether ketone, liquid crystalline polymer, further aliphatic polyketone, polyamide and/or polyoxymethylene.
  • the nozzle plate is usually part of a spinning pack, which consists of filter devices for the molten spinning mass and the downstream nozzle plate.
  • the temperature of the spinning mass must be chosen so that, on the one hand, sufficient flowability of the spinning mass is ensured and, on the other hand, that the thermal stress on the polyketone remains limited, so that crosslinking and degradation reactions as well as gel formation in the spinning mass are kept within limits or even completely suppressed can be.
  • a polyketone raw material stabilized with an antioxidant and a selected further polymer originating from the masterbatch are used.
  • the temperatures of the spinning mass as it exits through the spinning capillary can be in the range from 200 to 300 ° C, preferably from 220 to 240 ° C.
  • the diameter of a spinning capillary is selected by the expert based on the desired fiber weight. Typical diameters are in the range from 10 ⁇ m to 5 mm, for monofilaments or bristles preferably in the range from 0.1 to 1 mm. This information corresponds to the diameter of the hole on the exit side of the polymer mass.
  • Integrated into the spinning process are one or more stretches with thermal effects that give the thread the desired final properties. Such procedures are known to those skilled in the art.
  • the filament is preferably drawn several times, in particular with a total draw ratio in the range from 1:3 to 1:15, preferably in the range from 1:4 to 1:8.
  • the stretching stage(s) is followed by at least one relaxation stage (fixing stage).
  • the stretched filaments are thermally treated while maintaining the fiber tension, so that built-in tensions in the filament can be reduced.
  • the filaments produced are then fed to a suitable storage form, for example wound up or cut into staple fibers in a cutting device.
  • a polymer blend made of aliphatic polyketone and polyolefin, polyester, polyurethane, polyphenylene sulfide, polyphenylene sulfone, polyphenylene ether, polyphenylene ketone, polyphenylene ether ketone, liquid crystalline polymer and / or further aliphatic polyketone is spun or is spun through a conventional spinning capillary as described above aliphatic polyketone on the one hand and polyolefin, polyester, polyurethane, polyphenylene sulfide, polyphenylene sulfone, polyphenylene ether, polyphenylene ketone, polyphenylene ether ketone, liquid crystalline polymer, further aliphatic polyketone, polyamide and / or polyoxymethylene on the other hand are spun through a spinning capillary to produce multi-component filaments.
  • the method of the second embodiment corresponds to the procedure in the first embodiment of the
  • an antioxidant preferably sterically hindered, can be present in the polymer components phenol, be present; However, it can also be worked without the antioxidant.
  • the temperature of the spinning mass must be chosen so that, on the one hand, sufficient flowability of the spinning mass is ensured and, on the other hand, that the thermal load on the aliphatic polyketone and the other polymer component remains limited, so that crosslinking and degradation reactions as well as gel formation in the Spinning mass can be kept within limits or even suppressed completely.
  • polymer raw materials can be used that are not necessarily stabilized with antioxidants.
  • the temperatures of the spinning mass as it exits through the spinning capillary can be in the range from 200 to 300 ° C, preferably from 220 to 260 ° C.
  • a blend of aliphatic polyketone and polysiloxane particles and/or poly(meth)acrylate particles is spun through a conventional spinning capillary as described above.
  • the fibers according to the invention are preferably used for the production of textile surface constructions, in particular wovens, spiral wovens, laid or knitted fabrics. These textile surface constructions are particularly suitable for use in sieves or conveyor belts. Another important area of application is fibers for brushes or for oral hygiene and personal care, but also short-cut fibers in composite materials with, for example, concrete as a matrix material.
  • the invention therefore also relates to textile fabrics containing the fibers described above, in particular textile fabrics in the form of a woven fabric, knitted fabric, knitted fabric, braid or scrim.
  • the fibers according to the invention are characterized by a combination of excellent mechanical properties, such as high tensile moduli and good loop and knot strength, excellent bending recovery, and very good sliding properties as well as high abrasion resistance.
  • the invention also relates to the use of the fibers described above, particularly in the form of monofilaments, as paper machine clothing, in conveyor belts and in filtration screens.
  • various stabilizers such as antioxidants for thermal stabilization and/or hydrolysis stabilizers, are added to the fibers according to the invention.
  • the fibers according to the invention are used in the form of monofilaments as paper machine clothing in the sheet forming section and/or in the drying section of the paper machine.
  • These monofilaments are used, for example, in the deficit of forming fabrics in paper machines. This can be done 100% as a sub-weft and/or as a so-called alternating weft (alternating the mentioned monofilament with, for example, polyamide, polyester or polyphenylene sulfide monofilaments).
  • alternating weft alternating the mentioned monofilament with, for example, polyamide, polyester or polyphenylene sulfide monofilaments.
  • the aliphatic polyketone causes a significant reduction in sliding friction and thus a significant reduction in the drive power of the paper machine, which results in significant energy savings.
  • the monofilament according to the invention is more abrasion-resistant than comparable monofilaments made from polyethylene terephthalate, polybutylene terephthalate or polycyclohexane terephthalate or from polyamides without the use of aliphatic polyketone.
  • the fibers according to the invention are particularly preferably used in the form of filtration fabrics or knitted fabrics, as support for membranes with a wide mesh and high dimensional stability (e.g. as support for reverse osmosis membranes, which must withstand a continuous pressure of 50 bar), and as process fabrics for Production of paper and nonwovens.
  • the fibers according to the invention are well suited for the production of conveyor belts in which a combination of dimensional stability and good sliding properties is required.
  • fibers according to the invention are their use in brushes, in particular in toothbrushes.
  • the fibers according to the invention are generally used in the form of bristles.
  • the monofilaments are available in endless or cut form and combined into bundles or as brushes.
  • the sheath polymers were type M630A with a melting point (according to ASTM D3418) of 222°C or alternatively a low-melting variant, such as type M410F with a melting point (according to ASTM D3418) of 199°C or similar the type M620A with a melting point (according to ASTM D3418) of 207°C.
  • the core polymers were, for example, a semi-crystalline PET (polyethylene terephthalate) with a melting point of 254 ° C or a polycarbonate (such as Makrolon 2456 from Covestro) or an aliphatic polyketone with a high melting point (Type M630A from Hyosung) or a blend of these components.
  • a semi-crystalline PET polyethylene terephthalate
  • a polycarbonate such as Makrolon 2456 from Covestro
  • an aliphatic polyketone with a high melting point Type M630A from Hyosung
  • both components were co-extruded in one production step.
  • the core/shell ratio can be adjusted via the relative delivery rate, which here was 70/30.
  • the monofilament was stretched several times under the influence of temperature.
  • the overall draw ratio chosen was 1:3.7.
  • tissue structures have, for example, increased shear stability.
  • networked structures show thickenings at the crossing points. This property is of interest, for example, for liquid filtration due to its positive flow properties.
  • PET polyethylene terephthalate
  • Such a monofilament was co-extruded in one production step.
  • the core/shell ratio can be adjusted via the relative delivery rate, which here was 70/30.
  • the monofilament was stretched several times under the influence of temperature.
  • the overall draw ratio chosen was 1:4.3
  • the combination of PET and aliphatic polyketone in a monofilament combines the usual properties of PET with the surface properties of polyketone. This makes it possible to produce fabric structures that have a significantly reduced coefficient of friction and can therefore lead to energy savings when used in conveyor belts, for example.
  • the advantage of the PET core results from the processing properties of the monofilament in the weaving process, which are analogous to PET (e.g. identical floating).
  • Aliphatic polyketone - type M630A from Hyosung Polyketone - was used as the matrix polymer.
  • 1.0% by weight of polysiloxane beads - type PMSQ E+580 from Coating Products - with an average diameter of 8 ⁇ m were dispersed in the matrix polymer.
  • the monofilament obtained shows the following properties: Unit Value diameter mm 0.6 fineness dtex 3702 strength cN/tex 40.4 Elongation at break % 25.4 Thermal shrinkage (at 180°C for 10 min) % 14.7
  • Example 3 Aliphatic polyketone - type M630A from Hyosung Polyketone - was used as the matrix polymer.
  • the second polymer component was a liquid crystal polymer (LCP) - polyester made from hydroxybenzoic acid and hydroxynaphthalenecarboxylic acid Type Vectra A950 from Ticona added at 7%.
  • LCP liquid crystal polymer
  • the monofilament obtained showed the following properties: Unit Value diameter mm 0.5 fineness dtex 2568 strength cN/tex 47.3 Elongation at break % 18.5 Thermal shrinkage (at 180°C for 10 min) % 8.5
  • the polyketone was extruded, spun and stretched several times under the influence of temperature.

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  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
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Claims (21)

  1. Fibres filées à l'état fondu contenant une polycétone aliphatique thermoplastique comme premier polymère et une polyoléfine, un polyester, un polyamide, un polyoxyméthylène, un polyuréthane, un poly(sulfure de phénylène), une poly(sulfone de phénylène), un poly(éther de phénylène), un poly(cétone de phénylène), un poly(éther cétone de phénylène), un polymère cristallin liquide et/ou un polycétone aliphatique comme second polymère, les polymères se présentant sous la forme de deux ou plusieurs composants fibreux qui sont séparés dans l'espace les uns des autres mais disposés de manière contiguë les uns par rapport aux autres et, dans le cas où une polycétone aliphatique est contenue comme deuxième polymère, son point de fusion étant supérieur d'au moins 5 °C au point de fusion de la polycétone aliphatique du premier polymère.
  2. Fibres filées à chaud selon la revendication 1, caractérisées en ce que la polycétone aliphatique thermoplastique est présente sous forme de polymère matriciel et en ce que des particules de polysiloxanes ou de poly(méth)acrylates y sont dispersées.
  3. Fibres filées à l'état fondu selon l'une quelconque des revendications 1 à 2, caractérisées en ce que la polycétone aliphatique thermoplastique est un terpolymère éthylène/propylène/CO.
  4. Fibres filées à l'état fondu selon au moins l'une des revendications 1 à 3, caractérisées en ce que la fibre contient un antioxydant, de préférence un phénol stériquement encombré, éventuellement combiné à des co-stabilisants.
  5. Fibres filées à l'état fondu selon la revendication 1, caractérisées en ce que le polyester est un homopolymère ou un copolymère de polyester aromatique-aliphatique, en particulier un homopolymère de polyéthylène téréphtalate ou un copolymère contenant des unités d'éthylène téréphtalate.
  6. Fibres filées à l'état fondu selon la revendication 1, caractérisées en ce que le polyester est un polycarbonate.
  7. Fibres filées à l'état fondu selon au moins l'une des revendications 1 à 6, caractérisées en ce que le premier polymère et le deuxième polymère sont présents sous la forme d'un mélange de polymères, l'un des polymères formant une matrice et l'autre polymère étant dispersé dans la matrice sous la forme de fibrilles.
  8. Fibres filées à l'état fondu selon la revendication 7, caractérisées en ce que les fibres se présentent sous la forme de fibres en îlot dans la mer dans lesquelles un composant polymère est disposé sous la forme de fibrilles dans un composant de matrice polymère.
  9. Fibres filées à l'état fondu selon au moins l'une des revendications 1 à 8, caractérisées en ce qu'elles se présentent sous forme de fibres âme-gaine avec une gaine en polycétone aliphatique et avec une âme en polyoléfine, polyester, polyamide, polyoxyméthylène, polyuréthane, poly(sulfure de phénylène), poly(phénylène sulfone), poly(phénylène éther), poly(phénylène cétone), poly(phénylène éther cétone), polymère cristallin liquide et/ou une autre polycétone aliphatique.
  10. Fibres filées à l'état fondu selon la revendication 9, caractérisées en ce qu'elles se présentent sous forme de fibres âme-gaine avec une gaine en polycétone aliphatique et avec une âme en polyester, en sulfure de polyphénylène, en poly(phénylène éther), en poly(phénylène cétone), en poly(phénylène éther cétone) ou en une autre polycétone aliphatique.
  11. Fibres filées à l'état fondu selon la revendication 1, caractérisées en ce qu'elles se présentent sous forme de fibres côte à côte avec une partie de fibre en polycétone aliphatique et avec une autre partie de fibre en contact avec celle-ci en polyoléfine, polyester, polyamide, polyoxyméthylène, poly(sulfure de phénylène), poly(sulfone de phénylène), poly(éther de phénylène), poly(cétone de phénylène), poly(éther cétone de phénylène), polymère cristallin liquide et/ou une autre polycétone aliphatique.
  12. Fibres filées à l'état fondu selon la revendication 11, caractérisées en ce qu'elles se présentent sous forme de fibres côte à côte avec une partie de fibre en polycétone aliphatique et avec une autre partie de fibre en contact avec celle-ci en polyester, poly(sulfure de phénylène), poly(éther de phénylène), poly(cétone de phénylène) ou poly(éther cétone de phénylène).
  13. Fibres filées à l'état fondu selon au moins l'une des revendications 1 à 10, caractérisées en ce qu'elles sont réalisées sous forme de fibres à âme et gaine, comprennent une gaine en terpolymère thermoplastique éthylène/propylène/CO et une âme en polyoléfine, polyester, polyamide, polyoxyméthylène, poly(sulfure de phénylène), poly(sulfone de phénylène), poly(èther de phénylène), poly(cétone de phénylène), poly(éther cétone de phénylène), polymère cristallin liquide et/ou autre polycétone aliphatique, la masse de la gaine étant de 5 à 50 % en poids et la masse du âme étant de 95 à 5 % en poids, et où le âme et/ou la gaine peuvent éventuellement contenir encore au total jusqu'à 10 % en poids d'additifs, en particulier du phénol à empêchement stérique, des stabilisateurs UV, des pigments, des colorants, des matières de remplissage, des agents de matage, des agents de réticulation, des accélérateurs de cristallisation, des lubrifiants, des agents ignifuges, des agents antistatiques, des stabilisateurs d'hydrolyse, des plastifiants, des modificateurs de résistance aux chocs et/ou des fluoropolymères, les pourcentages se rapportant à la masse totale des fibres.
  14. Fibres filées à l'état fondu selon au moins l'une des revendications 1 à 13, caractérisées en ce qu'elles se présentent sous forme de monofilaments sans fin ou coupés et réunis en faisceaux ou sous forme de brosses.
  15. Structures textiles planes contenant les fibres filées à l'état fondu selon au moins l'une des revendications 1 à 14 sous la forme d'un tissu, d'un tricot, d'une maille, d'un tressage ou d'une tresse.
  16. Utilisation des fibres filées à l'état fondu selon au moins l'une des revendications 1 à 14 pour la fabrication de toiles de criblage, de toiles filtrantes pour filtres à gaz et à liquides, de bandes de process et de bandes de séchage et de brosses pour le nettoyage de tous types.
  17. Utilisation selon la revendication 16, caractérisée en ce que les fibres filées à l'état fondu sont utilisées comme bandes de fluidisation, comme bandes de traitement pour l'industrie du carton, comme bandes transporteuses et comme bandes de traitement dans la fabrication de non-tissés.
  18. Utilisation selon la revendication 16, caractérisée en ce que les fibres filées à l'état fondu sont utilisées dans des brosses à des fins de nettoyage dans le ménage ou dans les soins corporels, en particulier dans les brosses à dents.
  19. Utilisation selon la revendication 16, caractérisée en ce que les fibres filées à l'état fondu sont utilisées sous forme de fibres coupées court pour l'armature du béton et des composites.
  20. Utilisation selon la revendication 16, caractérisée en ce que les fibres filées à l'état fondu sont utilisées sous forme de monofilaments pour la garniture de machines à papier, dans des bandes transporteuses et dans des tamis de filtration.
  21. Utilisation selon la revendication 16, caractérisée en ce que les fibres filées à l'état fondu sont utilisées sous la forme de poils dans des brosses, en particulier dans des brosses à dents.
EP18728303.1A 2017-05-30 2018-05-18 Fibres de polycétone, leur preparation et leur utilisation Active EP3631057B1 (fr)

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DE202017002839.5U DE202017002839U1 (de) 2017-05-30 2017-05-30 Polyketonfasern, deren Herstellung und Verwendung
PCT/EP2018/000265 WO2018219494A1 (fr) 2017-05-30 2018-05-18 Fibres de polycétone, leur fabrication et leur utilisation

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EP3631057B1 true EP3631057B1 (fr) 2024-01-17

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CN110205707B (zh) * 2019-05-10 2021-09-21 海盐县硕创服装研究所 一种耐磨布料
CN110840066B (zh) * 2019-10-14 2022-04-05 安徽琼钰刷业有限公司 一种异形毛刷刷丝的生产工艺
CN111411417A (zh) * 2020-05-15 2020-07-14 天津工业大学 一种石墨烯增强聚酮纤维及其制备方法
CA3214300A1 (fr) * 2021-03-19 2022-09-22 Safari Belting Systems, Inc. Module transporteur dont de petits fragments sont detectables magnetiquement et aux rayons x
FI20215654A1 (en) * 2021-06-04 2022-12-05 Valmet Technologies Inc Monofilament thread
WO2023100943A1 (fr) * 2021-12-01 2023-06-08 旭化成株式会社 Feuille de fibres de résine, préimprégné et procédé de production de préimprégné

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PT3631056T (pt) 2021-10-07
JP2020521893A (ja) 2020-07-27
ES2891998T3 (es) 2022-02-01
WO2018219495A1 (fr) 2018-12-06
DE202017002839U1 (de) 2018-08-31
US20200080236A1 (en) 2020-03-12
EP3631056A1 (fr) 2020-04-08
EP3631057A1 (fr) 2020-04-08
WO2018219494A8 (fr) 2020-01-16
PL3631056T3 (pl) 2021-12-27
MX2019014377A (es) 2020-01-23
CN110678588A (zh) 2020-01-10
KR20200038427A (ko) 2020-04-13
EP3631056B1 (fr) 2021-06-30
FI3631057T3 (fi) 2024-03-25
WO2018219494A1 (fr) 2018-12-06

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